Process for preparing hydrogen peroxide from the elements

ABSTRACT

The present invention relates to a process for the preparation of hydrogen peroxide from oxygen or oxygen-delivering substances and hydrogen or hydrogen-delivering substances in the presence of at least one catalyst containing a metal-organic framework material, wherein said framework material comprises pores and a metal ion and an at least bidentate organic compound, said bidentate organic compound being coordinately bound to the metal ion. The invention further relates to a novel material consisting of said metal organic framework material wherein the material is brought in contact with at least one additional metal.

BACKGROUND AND SUMMARY OF THE INVENTION

1. Field of the Invention

The present invention relates to a process for preparing hydrogenperoxide from the reaction of oxygen and/or oxygen-delivering substanceswith hydrogen and/or hydrogen-delivering substances in the presence of acatalyst.

2. Discussion of the Background

Most hydrogen peroxide produced commercially is obtained via theanthraquinone process involving the oxidation of an anthra-hydroquinonein the presence of air (yielding the hydrogen peroxide) and therecycling reaction of reducing the resulting anthraquinone toanthra-hydroquinone in the presence of a noble metal catalyst, mostcommonly Pd. A catalyst free of noble metals is described in WO97/01113. The formation of hydrogen peroxide from the elements is not ofsignificant commercial importance at this point. However, for specificapplications, e.g. in electronics, ultrapure hydrogen peroxide isrequired. In this context, producing hydrogen peroxide from the elementsmay be cost-effective over working-up and cleaning hydrogen peroxideobtained by the anthraquinone process.

In a promising novel and alternative strategy to create micro- and/ormesoporous catalytically active materials in general, metal ions andmolecular organic building blocks are used to form so-calledmetal-organic frameworks (MOFs). The metal-organic framework materialsas such are described, for example, in. U.S. Pat. No. 5,648,508, EP-A-0709 253, M. O'Keeffe et al., J. Sol. State Chem., 152 (2000) p. 3–20, H.Li et al., Nature 402 (1999) p. 276 seq., M. Eddaoudi et al., Topics inCatalysis 9 (1999) p. 105–111, B. Chen et al., Science 291 (2001) p.1021–23.

Among the advantages of these novel materials, in particular forapplications in catalysis, are the following:

-   -   (i) larger pore sizes can be realized than for the zeolites used        presently;    -   (ii) the internal surface area is larger than for porous        materials used presently;    -   (iii) pore size and/or channel structure can be tailored over a        large range;    -   (iv) the organic framework components forming the internal        surface can be functionalized easily;    -   (v) the metal-organic framework according to the invention is        stable even if no host, solvent or any other additional        substance is present, i.e. the framework does not collapse        and/or interpenetrate and/or change its shape and dimension.        This puts the material according to the invention in contrast to        other metal-organic materials that maybe used as catalysts.

However, these novel porous materials have only been described as such.The use of these catalytically active materials for the reaction ofhydrogen and oxygen to form hydrogen peroxide has not been disclosedyet. In related applications, the use of these novel porous materials asshaped bodies (U.S. application Ser. No. 10/157,182) and for epoxidationreactions (U.S. application Ser. No. 10/157,494) has been described.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a process and acatalyst for the reaction of oxygen and/or oxygen-delivering substanceswith hydrogen and/or hydrogen-delivering substances, wherein thecatalyst for said reaction contains a novel material, in addition to, orinstead of, catalytic materials according to the prior art.

This object is solved by providing a process for the reaction of oxygenand/or oxygen-delivering substances with hydrogen and/orhydrogen-delivering substances in the presence of a catalyst, whereinsaid catalyst contains a metal-organic framework material comprisingpores and at least one metal ion and at least one at least bidentateorganic compound, which is coordinately bound to said metal ion, andwherein said framework material retains its dimension and shape evenwhile no other materials are present.

DETAILED DESCRIPTION OF THE INVENTION

As has been mentioned above, metal-organic framework materials as suchare described in, for example, U.S. Pat. No. 5,648,508, EP-A-0 709 253,M. O'Keeffe et al., J. Sol. State Chem., 152 (2000) p. 3–20, H. Li etal., Nature 402 (1999) p. 276 seq., M. Eddaoudi et al., Topics inCatalysis 9 (1999) p. 105–111, B. Chen et al., Science 291 (2001) p.1021–23. An inexpensive way for the preparation of said materials is thesubject of DE 10111230.0. The content of these publications, to whichreference is made herein, is fully incorporated in the content of thepresent application.

The catalyst used in the present invention contains at least onemetal-organic framework material, for example one of the materialsdescribed below.

The metal-organic framework materials, as used in the present invention,comprise pores, particularly micro- and/or mesopores. Micropores aredefined as being pores having a diameter of 2 nm or below and mesoporesas being pores having a diameter in the range of above 2 nm to 50 nm,respectively, according to the definition given in Pure Applied Chem.45, p. 71 seq., particularly on p. 79 (1976). The presence of the micro-and/or mesopores can be monitored by sorption measurements fordetermining the capacity of the metal-organic framework materials totake up nitrogen at 77 K according to DIN 66131 and/or DIN 66134.

For example, a type-I-form of the isothermal curve indicates thepresence of micropores {see, for example, paragraph 4 of M. Eddaoudi etal., Topics in Catalysis 9 (1999)}. In a preferred embodiment, thespecific surface area, as calculated according to the Langmuir model(DIN 66131, 66134) is above 5 m²/g, preferably above 10 m²/g, morepreferably above 50 m²/g, particularly preferred above 500 m²/g and mayincrease into the region of to above 3000 m 2/g.

As to the metal component within the framework material that is to beused according to the present invention, particularly to be mentionedare the metal ions of the main group elements and of the subgroupelements of the periodic system of the elements, namely of the groupsIa, IIa, IIIa, IVa to VIIIa and Ib to VIb. Among those metal components,particular reference is made to Mg, Ca, Sr, Ba, Sc, Y, Ti, Zr, Hf, V,Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag,Au, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi, morepreferably to Zn, Cu, Ni, Pd, Pt, Ru, Rh and Co. As to the metal ions ofthese elements, particular reference is made to: Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺,Sc³⁺, Y³⁺, Ti⁴⁺, Zr⁴⁺, Hf⁴⁺, V⁴⁺, V³⁺, V²⁺, Nb³⁺, Ta³⁺, Ta³⁺, Cr³⁺,Mo³⁺, W³⁺, Mn³⁺, Mn²⁺, Re³⁺, Re²⁺, Fe³⁺, Fe²⁺, Ru³⁺, Ru²⁺, Os³⁺, Os²⁺,Co³, Co²⁺, Rh²⁺, Ir²⁺, Ni²⁺, Ni⁺, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Ag⁺,Au⁺, Zn²⁺, Cd²⁺, Hg²⁺, Al³⁺, Ga³⁺, In³⁺, Tl³⁺, Si⁴⁺, Si²⁺, Ge⁴⁺, Ge²⁺,Sn⁴⁺, Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As⁺, Sb⁵⁺, Sb⁺, Bi⁵⁺, Bi³⁺, and Bi⁺.

With regard to the preferred metal ions and further details regardingthe same, particular reference is made to: EP-A 0 790 253, particularlyto p. 10, 1. 8–30, section “The Metal Ions”, which section isincorporated herein by reference. In the context of the presentinvention, Zn is particularly preferred as the metal component.

In addition to the metal salts disclosed in EP-A 0 790 253 and U.S. Pat.No. 5,648,508, other metallic compounds can be used, such as sulfates,phosphates and other complex counter-ion metal salts of the main- andsubgroup metals of the periodic system of the elements. Metal oxides,mixed oxides and mixtures of metal oxides and/or mixed oxides with orwithout a defined stoichiometry are preferred. All of the abovementioned metal compounds can be soluble or insoluble and they may beused as starting material either in form of a powder or as a shaped bodyor as any combination thereof.

As to the at least bidentate organic compound, which is capable tocoordinate with the metal ion, in principle all compounds can be usedwhich are suitable for this purpose and which fulfill the aboverequirements of being at least bidentate. Said organic compound musthave at least two centers, which are capable to coordinate with themetal ions of a metal salt, particularly with the metals of theaforementioned groups. With regard to the at least bidentate organiccompound, specific mention is to be made of compounds having

-   i) an alkyl group substructure, having from 1 to 10 carbon atoms,-   ii) an aryl group substructure, having from 1 to 5 phenyl rings,-   iii) an alkyl or aryl amine substructure, consisting of alkyl groups    having from 1 to 10 carbon atoms or aryl groups having from 1 to 5    phenyl rings,    said substructures having bound thereto at least one at least    bidentate functional group “X”, which is covalently bound to the    substructure of said compound, and wherein X is selected from the    group consisting of CO₂H, CS₂H, NO₂, SO₃H, Si(OH)₃, Ge(OH)₃,    Sn(OH)₃, Si(SH)₄, Ge(SH)₄, Sn(SH)₃, PO₃H, AsO₃H, AsO₄H, P(SH)₃,    As(SH)₃, CH(RSH)₂, C(RSH)₃, CH(RNH₂)₂, C(RNH₂)₃, CH(ROH)₂, C(ROH)₃,    CH(RCN)₂, C(RCN)₃, wherein R is an alkyl group having from 1 to 5    carbon atoms, or an aryl group consisting of 1 to 2 phenyl rings,    and CH(SH)₂, C(SH)₃, CH(NH₂)₂, C(NH₂)₂, CH(OH)₂, C(OH)₃, CH(CN)₂ and    C(CN)₃.

Particularly to be mentioned are substituted or unsubstituted, mono- orpolynuclear aromatic di-, tri- and tetracarboxylic acids and substitutedor unsubstituted, aromatic, at least one hetero atom comprising aromaticdi-, tri- and tetracarboxylic acids, which have one or more nuclei.Preferred bidendate organic compounds in the context of the presentinvention are alkyl group substructures with at least two carboxy groupsand/or aryl groups with one or two phenyl rings having at least twocarboxy groups.

A preferred ligand is 1,3,5-benzene tricarboxylate (BCT). Furtherpreferred ligands are ADC (acetylene dicarboxylate), NDC (naphtalendicarboxylate), BDC (benzene dicarboxylate), ATC (adamantanetetracarboxylate), BTC (benzene tricarboxylate), BTB (benzenetribenzoate), MTB (methane tetrabenzoate) and ATB (adamantanetribenzoate).

Besides the at least bidentate organic compound, the framework materialas used in accordance with the present invention may also comprise oneor more mono-dentate ligand(s), which is/are preferably selected fromthe following mono-dentate substances and/or derivatives thereof:

-   a. alkyl amines and their corresponding alkyl ammonium salts,    containing linear, branched, or cyclic aliphatic groups, having from    1 to 20 carbon atoms (and their corresponding ammonium salts);-   b. aryl amines and their corresponding aryl ammonium salts having    from 1 to 5 phenyl rings;-   c. alkyl phosphonium salts, containing linear, branched, or cyclic    aliphatic groups, having from 1 to 20 carbon atoms;-   d. aryl phosphonium salts, having from 1 to 5 phenyl rings;-   e. alkyl organic acids and the corresponding alkyl organic anions    (and salts) containing linear, branched, or cyclic aliphatic groups,    having from 1 to 20 carbon atoms;-   f. aryl organic acids and their corresponding aryl organic anions    and salts, having from 1 to 5 phenyl rings;-   g. aliphatic alcohols, containing linear, branched, or cyclic    aliphatic groups, having from 1 to 20 carbon atoms;-   h. aryl alcohols having from 1 to 5 phenyl rings;-   i. inorganic anions from the group consisting of: sulfate, nitrate,    nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate,    dihydrogen phosphate, diphosphate, triphosphate, phosphite,    chloride, chlorate, bromide, bromate, iodide, iodate, carbonate,    bicarbonate, and the corresponding acids and salts of the    aforementioned inorganic anions,-   j. ammonia, carbon dioxide, methane, oxygen, ethylene, hexane,    benzene, toluene, xylene, chlorobenzene, nitrobenzene, naphthalene,    thiophene, pyridine, acetone, 1-2-dichloroethane, methylenechloride,    tetrahydrofuran, ethanolamine, triethylamine and    trifluoromethylsulfonic acid.    Further details regarding the at least bidentate organic compounds    and the mono-dentate substances, from which the ligands of the    framework material as used in the present application are derived,    can be taken from EP-A 0 790 253, whose respective content is    incorporated into the present application by reference.

Within the present application, framework materials of the kinddescribed herein, which comprise Zn²⁺ as a metal ion and ligands derivedfrom terephthalic acid as the bidentate compound, are particularlypreferred. Said framework materials are known as MOF-5 in theliterature.

Further metal ions and at least bidentate organic compounds andmono-dentate substances, which are respectively useful for thepreparation of the framework materials used in the present invention aswell as processes for their preparation are particularly disclosed inEP-A 0 790 253, U.S. Pat. No. 5,648,508 and DE 10111230.0.

As solvents, which are particularly useful for the preparation of MOF-5,in addition to the solvents disclosed in the above-referencedliterature, dimethyl formamide, diethyl formamide andN-methylpyrollidone, alone, in combination with each other or incombination with other solvents may be used. Within the preparation ofthe framework materials, particularly within the preparation of MOF-5,the solvents and mother liquors are recycled after crystallization inorder to save costs and materials.

The pore sizes of the metal-organic framework can be adjusted byselecting suitable organic ligands and/or bidendate compounds(=linkers). Generally, the larger the linker, the larger the pore size.Any pore size that is still supported by a the metal-organic frameworkin the absence of a host and at temperatures of at least 200° C. isconceivable. Pore sizes ranging from 0.2 nm to 30 nm are preferred, withpore sizes ranging from 0.3 nm to 3 nm being particularly preferred.

In the following, examples of metal-organic framework materials (MOFs)are given to illustrate the general concept given above. These specificexamples, however, are not meant to limit the generality and scope ofthe present application.

By way of example, a list of metal-organic framework materials alreadysynthesized and characterized is given below. This also includes novelisoreticular metal organic framework materials (IR-MOFs), which may beused in the context of the present application. Such materials havingthe same framework topology while displaying different pore sizes andcrystal densities are described, for example in M. Eddouadi et al.,Science 295 (2002) 469, whose respective content is incorporated intothe present application by reference.

The solvents used are of particular importance for the synthesis ofthese materials and are therefore mentioned in the table. The values forthe cell parameters (angles α, β and γ as well as the spacings a, b andc, given in Angstrom) have been obtained by x-ray diffraction andrepresent the space group given in the table as well.

Ingredients molar ratios Space MOF-n M + L Solvents α β γ a b c GroupMOF-0 Zn(NO₃)₂.6H₂O ethanol 90 90 120 16.711 16.711 14.189 P6(3)/H₃(BTC) Mcm MOF-2 Zn(NO₃)₂.6H₂O DMF 90 102.8 90 6.718 15.49 12.43P2(1)/n (0.246 mmol) toluene H₂(BDC) 0.241 mmol) MOF-3 Zn(NO₃)₂.6H₂O DMF99.72 111.11 108.4 9.726 9.911 10.45 P-1 (1.89 mmol) MeOH H₂(BDC) (1.93mmol) MOF-4 Zn(NO₃)₂.6H₂O ethanol 90 90 90 14.728 14.728 14.728 P2(1)3(1.00 mmol) H₃(BTC) (0.5 mmol) MOF-5 Zn(NO₃)₂.6H₂O DMF 90 90 90 25.66925.669 25.669 Fm-3m (2.22 mmol) chloro- H₂(BDC) benzene (2.17 mmol)MOF-38 Zn(NO₃)₂.6H₂O DMF 90 90 90 20.657 20.657 17.84 14cm (0.27 mmol)chloro- H₃(BTC) benzene (0.15 mmol) MOF-31 Zn(NO₃)₂.6H₂O ethanol 90 9090 10.821 10.821 10.821 Pn(−3)m Zn(ADC)₂ 0.4 mmol H₂(ADC) 0.8 mmolMOF-12 Zn(NO₃)₂.6H₂O ethanol 90 90 90 15.745 16.907 18.167 Pbca Zn₂(ATC)0.3 mmol H₄(ATC) 0.15 mmol MOF-20 Zn(NO₃)₂.6H₂O DMF 90 92.13 90 8.1316.444 12.807 P2(1)/c ZnNDC 0.37 mmol chloro- H₂NDC benzene 0.36 mmolMOF-37 Zn(NO₃)₂.6H₂O DEF 72.38 83.16 84.33 9.952 11.576 15.556 P-1 0.2mmol chloro- H₂NDC benzene 0.2 mmol MOF-8 Tb(NO₃)₃.5H₂O DMSO 90 115.7 9019.83 9.822 19.183 C2/c Tb₂(ADC) 0.10 mmol MeOH H₂ADC 0.20 mmol MOF-9Tb(NO₃)₃.5H₂O DMSO 90 102.09 90 27.056 16.795 28.139 C2/c Tb₂(ADC) 0.08mmol H₂ADB 0.12 mmol MOF-6 Tb(NO₃)₃.5H₂O DMF 90 91.28 90 17.599 19.99610.545 P21/c 0.30 mmol MeOH H₂(BDC) 0.30 mmol MOF-7 Tb(NO₃)₃.5H₂O H₂O102.3 91.12 101.5 6.142 10.069 10.096 P-1 0.15 mmol H₂(BDC) 0.15 mmolMOF-69A Zn(NO₃)₂.6H₂O DEF 90 111.6 90 23.12 20.92 12 C2/c 0.083 mmolH₂O₂ 4,4′BPDC MeNH₂ 0.041 mmol MOF-69B Zn(NO₃)₂.6H₂O DEF 90 95.3 9020.17 18.55 12.16 C2/c 0.083 mmol H₂O₂ 2,6-NCD MeNH₂ 0.041 mmol MOF-11Cu(NO₃)₂.2.5H₂O H₂O 90 93.86 90 12.987 11.22 11.336 C2/c Cu₂(ATC) 0.47mmol H₂ATC 0.22 mmol MOF-11 90 90 90 8.4671 8.4671 14.44 P42/ Cu₂(ATC)mmc dehydr. MOF-14 Cu(NO₃)₂.2.5H₂O H₂O 90 90 90 26.946 26.946 26.946Im-3 Cu₃(BTB) 0.28 mmol DMF H₃BTB EtOH 0.052 mmol MOF-32 Cd(NO₃)₂.4H₂OH₂O 90 90 90 13.468 13.468 13.468 P(−4)3m Cd(ATC) 0.24 mmol NaOH H₄ATC0.10 mmol MOF-33 ZnCl₂ H₂O 90 90 90 19.561 15.255 23.404 Imma Zn₂(ATB)0.15 mmol DMF H₄ATB EtOH 0.02 mmol MOF-34 Ni(NO₃)₂.6H₂O H₂O 90 90 9010.066 11.163 19.201 P2₁2₁2₁ Ni(ATC) 0.24 mmol NaOH H₄ATC 0.10 mmolMOF-36 Zn(NO₃)₂.4H₂O H₂O 90 90 90 15.745 16.907 18.167 Pbca Zn₂(MTB)0.20 mmol DMF H₄MTB 0.04 mmol MOF-39 Zn(NO₃)₂.4H₂O H₂O 90 90 90 17.15821.591 25.308 Pnma Zn₃O(HBTB) 0.27 mmol DMF H₃BTB EtOH 0.07 mmol NO305FeCl₂.4H₂O DMF 90 90 120 8.2692 8.2692 63.566 R-3c 5.03 mmol formic acid86.90 mmol NO306A FeCl₂.4H₂O DEF 90 90 90 9.9364 18.374 18.374 Pbcn 5.03mmol formic acid 86.90 mmol NO29 Mn(Ac)₂.4H₂O DMF 120 90 90 14.16 33.52133.521 P-1 MOF-0 like 0.46 mmol H₃BTC 0.69 mmol BPR48A2 Zn(NO₃)₂.6H₂ODMSO 90 90 90 14.5 17.04 18.02 Pbca 0.012 mmol toluene H₂BDC 0.012 mmolBPR69 Cd(NO₃)₂.4H₂O DMSO 90 98.76 90 14.16 15.72 17.66 Cc B1 0.0212 mmolH₂BDC 0.0428 mmol BPR92A2 Co(NO₃)₂.6H₂O NMP 106.3 107.63 107.2 7.530810.942 11.025 P1 0.018 mmol H₂BDC 0.018 mmol BPR95 Cd(NO₃)₂.4H₂O NMP 90112.8 90 14.460 11.085 15.829 P2(1)/n C5 0.012 mmol H₂BDC 0.36 mmol CuC₆H₄O₆ Cu(NO₃)₂.2.5H₂O DMF 90 105.29 90 15.259 14.816 14.13 P2(1)/c0.370 mmol chloro- H₂BDC(OH)₂ benzene 0.37 mmol M(BTC) Co(SO₄).H₂O DMFSame as MOF-0 MOF-0 like 0.055 mmol H₃BTC 0.037 mmol Tb(C₆H₄O₆)Tb(NO₃)₃.5H₂O DMF 104.6 107.9 97.147 10.491 10.981 12.541 P-1 0.370 mmolchloro- H₂(C₆H₄O₆) benzene 0.56 mmol Zn (C₂O₄) ZnCl₂ DMF 90 120 909.4168 9.4168 8.464 P(−3)1m 0.370 mmol chloro- oxalic acid benzene 0.37mmol Co(CHO) Co(NO₃)₂.5H₂O DMF 90 91.32 90 11.328 10.049 14.854 P2(1)/n0.043 mmol formic acid 1.60 mmol Cd(CHO) Cd(NO₃)₂.4H₂O DMF 90 120 908.5168 8.5168 22.674 R-3c 0.185 mmol formic acid 0.185 mmol Cu(C₃H₂O₄)Cu(NO₃)₂.2.5H₂O DMF 90 90 90 8.366 8.366 11.919 P43 0.043 mmol malonicacid 0.192 mmol Zn₆(NDC)₅ Zn(NO₃)₂.6H₂O DMF 90 95.902 90 19.504 16.48214.64 C2/m MOF-48 0.097 mmol chloro- 14 NDC benzene 0.069 mmol H₂O₂MOF-47 Zn(NO₃)₂.6H₂O DMF 90 92.55 90 11.303 16.029 17.535 P2(1)/c 0.185mmol chloro- H₂(BDC[CH₃]₄) benzene 0.185 mmol H₂O₂ MO25 Cu(NO₃)₂.2.5H₂ODMF 90 112.0 90 23.880 16.834 18.389 P2(1)/c 0.084 mmol BPhDC 0.085 mmolCu-Thio Cu(NO₃)₂.2.5H₂O DEF 90 113.6 90 15.4747 14.514 14.032 P2(1)/c0.084 mmol thiophene dicarboxylic 0.085 mmol C1BDC1 Cu(NO₃)₂.2.5H₂O DMF90 105.6 90 14.911 15.622 18.413 C2/c 0.084 mmol H₂(BDCCl₂) 0.085 mmolMOF-101 Cu(NO₃)₂.2.5H₂O DMF 90 90 90 21.607 20.607 20.073 Fm3m 0.084mmol BrBDC 0.085 mmol Zn₃(BTC)₂ ZnCl₂ DMF 90 90 90 26.572 26.572 26.572Fm-3m 0.033 mmol EtOH H₃BTC base 0.033 mmol added MOF-j Co(CH₃CO₂)₂.4H₂OH₂O 90 112.0 90 17.482 12.963 6.559 C2 (1.65 mmol) H₃(BZC) (0.95 mmol)MOF-n Zn(NO₃)₂.6H₂O ethanol 90 90 120 16.711 16.711 14.189 P6(3)/H₃(BTC) mcm PbBDC Pb(NO₃)₂ DMF 90 102.7 90 8.3639 17.991 9.9617 P2(1)/n(0.181 mmol) ethanol H₂(BDC) (0.181 mmol) Znhex Zn(NO₃)₂.6H₂O DMF 90 90120 37.1165 37.117 30.019 P3(1)c (0.171 mmol) p-xylene H₃BTB ethanol(0.114 mmol) AS16 FeBr₂ DMF 90 90.13 90 7.2595 8.7894 19.484 P2(1)c0.927 mmol anhydr. H₂(BDC) 0.927 mmol AS27-2 FeBr₂ DMF 90 90 90 26.73526.735 26.735 Fm3m 0.927 mmol anhydr. H₃(BDC) 0.464 mmol AS32 FeCl₃ DMF90 90 120 12.535 12.535 18.479 P6(2)c 1.23 mmol anhydr. H₂(BDC) ethanol1.23 mmol AS54-3 FeBr₂ DMF 90 109.98 90 12.019 15.286 14.399 C2 0.927anhydr. BPDC n- 0.927 mmol propanol AS61-4 FeBr₂ pyridine 90 90 12013.017 13.017 14.896 P6(2)c 0.927 mmol anhydr. m-BDC 0.927 mmol AS68-7FeBr₂ DMF 90 90 90 18.3407 10.036 18.039 Pca2₁ 0.927 mmol anhydr. m-BDCPyridine 1.204 mmol Zn(ADC) Zn(NO₃)₂.6H₂O DMF 90 99.85 90 16.764 9.3499.635 C2/c 0.37 mmol chloro- H₂(ADC) benzene 0.36 mmol MOF-12Zn(NO₃)₂.6H₂O ethanol 90 90 90 15.745 16.907 18.167 Pbca Zn₂(ATC) 0.30mmol H₄(ATC) 0.15 mmol MOF-20 Zn(NO₃)₂.6H₂O DMF 90 92.13 90 8.13 16.44412.807 P2(1)/c ZnNDC 0.37 mmol chloro- H₂NDC benzene 0.36 mmol MOF-37Zn(NO₃)₂.6H₂O DEF 72.38 83.16 84.33 9.952 11.576 15.556 P-1 0.20 mmolchloro- H₂NDC benzene 0.20 mmol Zn(NDC) Zn(NO₃)₂.6H₂O DMSO 68.08 75.3388.31 8.631 10.207 13.114 P-1 (DMSO) H₂NDC Zn(NDC) Zn(NO₃)₂.6H₂O 90 99.290 19.289 17.628 15.052 C2/c H₂NDC Zn(HPDC) Zn(NO₃)₂.4H₂O DMF 107.9105.06 94.4 8.326 12.085 13.767 P-1 0.23 mmol H₂O H₂(HPDC) 0.05 mmolCo(HPDC) Co(NO₃)₂.6H₂O DMF 90 97.69 90 29.677 9.63 7.981 C2/c 0.21 mmolH₂O/ H₂(HPDC) ethanol 0.06 mmol Zn₃(PDC)2. Zn(NO₃)₂.4H₂O DMF/ CIBz 79.3480.8 85.83 8.564 14.046 26.428 P-1 5 0.17 mmol H₂O/ TEA H₂(HPDC) 0.05mmol Cd₂ Cd(NO₃)₂.4H₂O methanol/ 70.59 72.75 87.14 10.102 14.412 14.964P-1 (TPDC)2 0.06 mmol CHP H₂O H₂(HPDC) 0.06 mmol Tb(PDC)1.5Tb(NO₃)₃.5H₂O DMF 109.8 103.61 100.14 9.829 12.11 14.628 P-1 0.21 mmolH₂O/ H₂(PDC) ethanol 0.034 mmol ZnDBP Zn(NO₃)₂.6H₂O MeOH 90 93.67 909.254 10.762 27.93 P2/n 0.05 mmol dibenzylphosphate 0.10 mmol Zn₃(BPDC)ZnBr₂ DMF 90 102.76 90 11.49 14.79 19.18 P21/n 0.021 mmol 4,4'BPDC 0.005mmol CdBDC Cd(NO₃)₂.4H₂O DMF 90 95.85 90 11.2 11.11 16.71 P21/n 0.100mmol Na₂SiO₃ H₂(BDC) (aq) 0.401 mmol Cd-mBDC Cd(NO₃)₂.4H₂O DMF 90 101.190 13.69 18.25 14.91 C2/c 0.009 mmol MeNH₂ H₂(mBDC) 0.018 mmol Zn₄OBNDCZn(NO₃)₂.6H₂O DEF 90 90 90 22.35 26.05 59.56 Fmmm 0.041 mmol MeNH₂ BNDCH₂O₂ Eu(TCA) Eu(NO₃)₃.6H₂O DMF 90 90 90 23.325 23.325 23.325 Pm-3n 0.14mmol chloro- TCA benzene 0.026 mmol Tb(TCA) Tb(NO₃)₃.6H₂O DMF 90 90 9023.272 23.272 23.372 Pm-3n 0.069 mmol chloro- TCA benzene 0.026 mmolFormate Ce(NO₃)₃.6H₂O H₂O 90 90 120 10.668 10.667 4.107 R-3m 0.138 mmolethanol Formaic acid 0.43 mmol FeCl₂.4H₂O DMF 90 90 120 8.2692 8.269263.566 R-3c 5.03 mmol Formic acid 86.90 mmol FeCl₂.4H₂O DEF 90 90 909.9364 18.374 18.374 Pbcn 5.03 mmol Formic acid 86.90 mmol FeCl₂.4H₂ODEF 90 90 90 8.335 8.335 13.34 P-31c 5.03 mmol Formic acid 86.90 mmolNO330 FeCl₂.4H₂O form- 90 90 90 8.7749 11.655 8.3297 Pnna 0.50 mmolamide Formic acid 8.69 mmol NO332 FeCl₂.4H₂O DIP 90 90 90 10.0313 18.80818.355 Pbcn 0.50 mmol Formic acid 8.69 mmol NO333 FeCl₂.4H₂O DBF 90 9090 45.2754 23.861 12.441 Cmcm 0.50 mmol Formic acid 8.69 mmol NO335FeCl₂.4H₂O CHF 90 91.372 90 11.5964 10.187 14.945 P21/n 0.50 mmol Formicacid 8.69 mmol NO336 FeCl₂.4H₂O MFA 90 90 90 11.7945 48.843 8.4136 Pbcm0.50 mmol Formic acid 8.69 mmol NO13 Mn(Ac)₂.4H₂O ethanol 90 90 90 18.6611.762 9.418 Pbcn 0.46 mmol Bezoic acid 0.92 mmol Bipyridine 0.46 mmolNO29 Mn(Ac)₂.4H₂O DMF 120 90 90 14.16 33.521 33.521 P-1 MOF-0 like 0.46mmol H₃BTC 0.69 mmol Mn(hfac)₂ Mn(Ac)₂.4H₂O ether 90 95.32 90 9.57217.162 14.041 C2/c (O₂CC₆H₅) 0.46 mmol Hfac 0.92 mmol Bipyridine 0.46mmol BPR43G2 Zn(NO₃)₂.6H₂O DMF 90 91.37 90 17.96 6.38 7.19 C2/c 0.0288mmol CH₃CN H₂BDC 0.0072 mmol BPR48A2 Zn(NO₃)₂.6H₂O DMSO 90 90 90 14.517.04 18.02 Pbca 0.012 mmol toluene H₂BDC 0.012 mmol BPR49B1Zn(NO₃)₂.6H₂O DMSO 90 91.172 90 33.181 9.824 17.884 C2/c 0.024 mmolmethanol H₂BDC 0.048 mmol BPR56E1 Zn(NO₃)₂.6H₂O DMSO 90 90.096 9014.5873 14.153 17.183 P2(1)/n 0.012 mmol n- H₂BDC propanol 0.024 mmolBPR68D10 Zn(NO₃)₂.6H₂O DMSO 90 95.316 90 10.0627 10.17 16.413 P2(1)/c0.0016 mmol benzene H₃BTC 0.0064 mmol BPR69B1 Cd(NO₃)₂.4H₂O DMSO 9098.76 90 14.16 15.72 17.66 Cc 0.0212 mmol H₂BDC 0.0428 mmol BPR73E4Cd(NO₃)₂.4H₂O DMSO 90 92.324 90 8.7231 7.0568 18.438 P2(1)/n 0.006 mmoltoluene H₂BDC 0.003 mmol BPR76D5 Zn(NO₃)₂.6H₂O DMSO 90 104.17 90 14.41916.2599 7.0611 Pc 0.0009 mmol H₂BzPDC 0.0036 mmol BPR80B5 Cd(NO₃)₂.4H₂ODMF 90 115.11 90 28.049 9.184 17.837 C2/c 0.018 mmol H₂BDC 0.036 mmolBPR80H5 Cd(NO₃)₂.4H₂O DMF 90 119.06 90 11.4746 6.2151 17.268 P2/c 0.027mmol H₂BDC 0.027 mmol BPR82C6 Cd(NO₃)₂.4H₂O DMF 90 90 90 9.7721 21.14227.77 Fdd2 0.0068 mmol H₂BDC 0.202 mmol BPR86C3 Co(NO₃)₂.6H₂O DMF 90 9090 18.3449 10.031 17.983 Pca2(1) 0.0025 mmol H₂BDC 0.075 mmol BPR86H6Cd(NO₃)₂.6H₂O DMF 80.98 89.69 83.412 9.8752 10.263 15.362 P-1 0.010 mmolH₂BDC 0.010 mmol Co(NO₃)₂.6H₂O NMP 106.3 107.63 107.2 7.5308 10.94211.025 P1 BPR95A2 Zn(NO₃)₂.6H₂O NMP 90 102.9 90 7.4502 13.767 12.713P2(1)/c 0.012 mmol H₂BDC 0.012 mmol CuC₆F₄O₄ Cu(NO₃)₂.2.5H₂O DMF 9098.834 90 10.9675 24.43 22.553 P2(1)/n 0.370 mmol chloro- H₂BDC(OH) 2benzene 0.37 mmol Fe Formic FeCl₂.4H₂O DMF 90 91.543 90 11.495 9.96314.48 P2(1)/n 0.370 mmol Formic acid 0.37 mmol Mg Formic Mg(NO₃)₂.6H₂ODMF 90 91.359 90 11.383 9.932 14.656 P2(1)/n 0.370 mmol Formic acid 0.37mmol MgC₆H₄O₆ Mg(NO₃)₂.6H₂O DMF 90 96.624 90 17.245 9.943 9.273 C2/c0.370 mmol H₂BDC(OH)₂ 0.37 mmol Zn ZnCl₂ DMF 90 94.714 90 7.3386 16.83412.52 P2(1)/n C₂H₄BDC 0.44 mmol MOF-38 CBBDC 0.261 mmol MOF-49 ZnCl₂ DMF90 93.459 90 13.509 11.984 27.039 P2/c 0.44 mmol CH3CN m-BDC 0.261 mmolMOF-26 Cu(NO₃)₂.5H₂O DMF 90 95.607 90 20.8797 16.017 26.176 P2(1)/n0.084 mmol DCPE 0.085 mmol MOF-112 Cu(NO₃)₂.2.5H₂O DMF 90 107.49 9029.3241 21.297 18.069 C2/c 0.084 mmol ethanol o-Br-m-BDC 0.085 mmolMOF-109 Cu(NO₃)₂.2.5H₂O DMF 90 111.98 90 23.8801 16.834 18.389 P2(1)/c0.084 mmol KDB 0.085 mmol MOF-111 Cu(NO₃)₂.2.5H₂O DMF 90 102.16 9010.6767 18.781 21.052 C2/c 0.084 mmol ethanol o-BrBDC 0.085 mmol MOF-110Cu(NO₃)₂.2.5H₂O DMF 90 90 120 20.0652 20.065 20.747 R-3/m 0.084 mmolthiophene dicarboxylic 0.085 mmol MOF-107 Cu(NO₃)₂.2.5H₂O DEF 104.897.075 95.206 11.032 18.067 18.452 P-1 0.084 mmol thiophene dicarboxylic0.085 mmol MOF-108 Cu(NO₃)₂.2.5H₂O DBF/ 90 113.63 90 15.4747 14.51414.032 C2/c 0.084 mmol methanol thiophene dicarboxylic 0.085 mmolMOF-102 Cu(NO₃)₂.2.5H₂O DMF 91.63 106.24 112.01 9.3845 10.794 10.831 P-10.084 mmol H₂(BDCCl₂) 0.085 mmol Clbdcl Cu(NO₃)₂.2.5H₂O DEF 90 105.56 9014.911 15.622 18.413 P-1 0.084 mmol H₂(BDCCl₂) 0.085 mmol Cu(NMOP)Cu(NO₃)₂.2.5H₂O DMF 90 102.37 90 14.9238 18.727 15.529 P2(1)/m 0.084mmol NBDC 0.085 mmol Tb(BTC) Tb(NO₃)₃.5H₂O DMF 90 106.02 90 18.698611.368 19.721 0.033 mmol H₃BTC 0.033 mmol Zn₃(BTC)₂ ZnCl₂ DMF 90 90 9026.572 26.572 26.572 Fm-3m Honk 0.033 mmol ethanol H₃BTC 0.033 mmolZn₄O(NDC) Zn(NO₃)₂.4H₂O DMF 90 90 90 41.5594 18.818 17.574 aba2 0.066mmol ethanol 14NDC 0.066 mmol CdTDC Cd(NO₃)₂.4H₂O DMF 90 90 90 12.17310.485 7.33 Pmma 0.014 mmol H₂O thiophene 0.040 mmol DABCO 0.020 mmolIRMOF-2 Zn(NO₃)₂.4H₂O DEF 90 90 90 25.772 25.772 25.772 Fm-3m 0.160 mmolo-Br-BDC 0.60 mmol IRMOF-3 Zn(NO₃)₂.4H₂O DEF 90 90 90 25.747 25.74725.747 Fm-3m 0.20 mmol ethanol H₂N—BDC 0.60 mmol IRMOF-4 Zn(NO₃)₂.4H₂ODEF 90 90 90 25.849 25.849 25.849 Fm-3m 0.11 mmol [C₃H₇O]₂—BDC 0.48 mmolIRMOF-5 Zn(NO₃)₂.4H₂O DEF 90 90 90 12.882 12.882 12.882 Pm-3m 0.13 mmol[C₅H₁₁O]₂—BDC 0.50 mmol IRMOF-6 Zn(NO₃)₂.4H₂O DEF 90 90 90 25.842 25.84225.842 Fm-3m 0.20 mmol [C₂H₄]—BDC 0.60 mmol IRMOF-7 Zn(NO₃)₂.4H₂O DEF 9090 90 12.914 12.914 12.914 Pm-3m 0.07 mmol 1,4NDC 0.20 mmol IRMOF-8Zn(NO₃)₂.4H₂O DEF 90 90 90 30.092 30.092 30.092 Fm-3m 0.55 mmol 2,6NDC0.42 mmol IRMOF-9 Zn(NO₃)₂.4H₂O DEF 90 90 90 17.147 23.322 25.255 Pnnm0.05 mmol BPDC 0.42 mmol IRMOF-10 Zn(NO₃)₂.4H₂O DEF 90 90 90 34.28134.281 34.281 Fm-3m 0.02 mmol BPDC 0.012 mmol IRMOF-11 Zn(NO₃)₂.4H₂O DEF90 90 90 24.822 24.822 56.734 R-3m 0.05 mmol HPDC 0.20 mmol IRMOF-12Zn(NO₃)₂.4H₂O DEF 90 90 90 34.281 34.281 34.281 Fm-3m 0.017 mmol HPDC0.12 mmol IRMOF-13 Zn(NO₃)₂.4H₂O DEF 90 90 90 24.822 24.822 56.734 R-3m0.048 mmol PDC 0.31 mmol IRMOF-14 Zn(NO₃)₂.4H₂O DEF 90 90 90 34.38134.381 34.381 Fm-3m 0.17 mmol PDC 0.12 mmol IRMOF-15 Zn(NO₃)₂.4H₂O DEF90 90 90 21.459 21.459 21.459 Im-3m 0.063 mmol TPDC 0.025 mmol IRMOF-16Zn(NO₃)₂.4H₂O DEF 90 90 90 21.49 21.49 21.49 Pm-3m 0.0126 mmol NMP TPDC0.05 mmol

ADC Acetylene dicarboxylic acid NDC Naphtalene dicarboxylic acid BDCBenzene dicarboxylic acid ATC Adamantane tetracarboxylic acid BTCBenzene tricarboxylic acid BTB Benzene tribenzoate MTB Methanetetrabenzoate ATB Adamantane tetrabenzoate ADB Adamantane dibenzoate

Examples of the synthesis of these materials as such can, for example,be found in: J. Am. Chem. Soc. 123 (2001) pages 8241 ff or in Acc. Chem.Res. 31 (1998) pages 474ff, which are fully encompassed within thecontent of the present application.

The separation of the framework materials, particularly of MOF-5, fromthe mother liquor of the crystallization may be achieved by proceduresknown in the art such as solid-liquid separations, centrifugation,extraction, filtration, membrane filtration, cross-flow filtration,flocculation using flocculation adjuvants (non-ionic, cationic andanionic adjuvants) or by the addition of pH shifting additives such assalts, acids or bases, by flotation, as well as by evaporation of themother liquor at elevated temperature and/or in vacuo and concentratingof the solid. The material obtained in this step is typically a finepowder and is not optimally suited for most practical applications, e.g.in catalysis, where shaped bodies are preferred. Therefore, the powderis pressed or granulated or formed by any process known to the expert inthe art, in particular any process that results in forming a powder intoa shaped body. Such a process is disclosed, e.g. in the U.S. applicationSer. No. 10/157,182.

In a preferred embodiment, the metal-organic framework material catalystused for the reaction of oxygen and/or oxygen-delivering substances withhydrogen and/or hydrogen-delivering substances contains at least oneadditional metal selected from the main groups and/or the subgroups ofthe periodic table of the elements. In a further preferred embodiment,in order to produce said catalyst, the metal-organic framework materialas described above is brought in contact with a substance, preferably apowder, a solution or a suspension, containing at least one metal of themain groups or the subgroups of the periodic table of the elements.

The term “bringing in contact” in the context of the present inventionrefers to any procedure yielding a metal-organic framework catalyst asdescribed above, containing, at least in parts, at least one additionalmetal component. As far as the methods of bringing the metal-organicframework in contact with an additional metal component, any methodknown to the expert in the field, in particular any method known in thecontext of charging a porous material, can be used. In a preferredembodiment, these methods include but are not limited to: dipping,coating, spraying, impregnating, soaking, applying, precipitating,co-precipitating, kneading, powder kneading.

The additional metal is selected form the group consisting of the maingroup or the subgroup metals of the periodic table of the elements,preferably form the group of the sub group metals, further preferredfrom the group of Cu, Ag, Au, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt,particularly preferred from the group of Pd, Pt, Au. Mixtures of atleast two of all of the aforementioned substances are included as well.

For the reaction to produce hydrogen peroxide, any substance thatcontains or delivers oxygen and any substance that contains or delivershydrogen can be used, so long as, ultimately, hydrogen peroxide isformed in the presence of the catalyst according to the invention. In apreferred embodiment the molecular gases oxygen and hydrogen are used.Either or both gases may be mixed with other reactive gases and/or inertgases, preferably with inert gases.

The invention is now further described by way of the following examples,which are, however, not meant to limit the scope of the presentapplication.

EXAMPLES Example 1 Preparation of the Metal-Organic Framework Material

41 g of terephthalic acid are dissolved together with 193.5 g of ZnNO₃.4H₂O in 5650 g of diethyl formamide in a container with a frit (HWS, 10liters). The mixture is heated to 130° C. and kept at that temperaturefor 210 minutes. Subsequently, the mixture is cooled down and the solidformed is filtered off and washed three times with 1 liter ofchloroform, respectively. The filter cake is blow dried with nitrogen.

The product thusly obtained is subsequently activated in severalportions under high vacuum. The structure of MOF-5 is discernible in thex-ray diffraction pattern.

Example 2 Preparation of the Catalyst

The preparation of the metal-organic framework material containing Pdand used as a catalyst was performed as described in the following: 1.0g of Pd Acetate (4.45 mmol) are dissolved in 91.5 g of diethyl formamideand 33 g of acetonitrile in a beaker. The brownish solution is filledinto a four neck flask containing 5.0 g of the MOF-5 from Example 1. Thesuspension is cooked in an oil bath at 60° C. for 7 h while beingstirred. Subsequently the mixture is transferred into a beaker and themother liquor is decanted off after the crystals have settled.

The crystals are over-layered with chloroform and, after 12 hours,washed with chloroform until the chloroform solution hardly shows anycoloring, then transferred into a flask and dried at room temperatureunder high vacuum (turbo molecular pump). The yield was 5.7 g. Elementalanalysis resulted in a Pd content of 1.6% by weight next to 29.2% byweight of Zn and a residual content of Cl of 220 ppm.

Example 3 Activation of the Inventive Catalyst

54.3 g of the catalyst prepared as described above are transferred intoa glass reactor that is fed with 10% by volume of hydrogen in Ar at aflow rate of 30 ml/min. In a temperature-controlled reduction (AutochemII 2920, Micromeritics), the reactor is heated to 250° C. using a rampof 5 K/min. At a temperature of 92° C., 3.67 ml STP of gas per gram ofcatalyst are activated in the presence of hydrogen, corresponding toapprox. 1.7% by weight of Pd in the catalyst that can be reduced.

Example 4 Preparation of H₂O₂ Using the Inventive Catalyst

4 g of the material from Example 3 are mixed with 120 mg of Graphite andpressed into tablets of 4.75 mm over 3 mm using a tabletting apparatus(Korsch).

10 ml of these tablets are exposed to the following feed in a designatedpressure container with a basket-like insert: 89 g/h of methanolcontaining 120 ppm of NaBr, 8 STDl/h of hydrogen and 37.4 STDl/h ofoxygen. The liquid medium is stirred at 1500 rpm. A space-time yield of16 g/l/h with respect to the formation of hydrogen peroxide was measuredby means of titration at a temperature of 40° C., a pressure of 50 barand a running time of 91 hours.

1. A process for preparing hydrogen peroxide comprising: reacting oxygenor an oxygen-delivering substance with hydrogen or a hydrogen deliveringsubstance, in the presence of a catalyst, wherein the catalyst comprisesa metal-organic framework material having pores and comprising at leastone metal ion and at least one at least bidentate organic compoundcoordinately bound to the metal ion and wherein the metal-organicframework material further comprises at least one additional metalselected from the group consisting of metals of groups Ia, IIa, IIIa,IVa to VIIIa and Ib to IIIb of the periodic table.
 2. The process ofclaim 1, wherein the metal ion of the metal-organic framework catalystcomprises an ion selected from group consisting of Mg²⁺, Ca²⁺, Sc³⁺,Y³⁺, Ti⁴⁺, Zr⁴⁺, Hf⁴⁺, V⁴⁺, V³⁺, V²⁺, Nb³⁺, Ta³⁺, Cr³⁺, Mo³⁺, W³⁺, Mn³⁺,Mn²⁺, Re³⁺, Re²⁺, Fe³⁺, Fe²⁺, Ru³⁺, Ru²⁺, Os³⁺, Os²⁺, Co³⁺, Co²⁺, Rh²⁺,Rh⁺, Ir²⁺, Ir⁺, Ni²⁺, Ni⁺, Pd²⁺, Pd⁺, Pt²⁺, Pt⁺, Cu²⁺, Cu⁺, Ag⁺, Au⁺,Zn²⁺, Cd²⁺, Hg²⁺, Al³⁺, Ga³⁺, In³⁺, Tl³⁺, Si⁴⁺, Si²⁺, Ge⁴⁺, Ge²⁺, Sn⁴⁺,Sn²⁺, Pb⁴⁺, Pb²⁺, As⁵⁺, As³⁺, As⁺, Sb⁵⁺, Sb³⁺, Sb⁺, Bi⁵⁺, Bi³⁺, and Bi⁺.3. The process of claim 2, wherein the metal ion is Zn²⁺.
 4. The processof claim 1, wherein the at least bidentate organic compound has asubstructure bound to at least one bidentate functional group, saidsubstructure is selected from the group consisting of alkyl groups, anaryl group having 1 of 2 phenyl rings, and combinations thereof, andsaid bidentate functional group has at least 2 carboxy groups.
 5. Theprocess of claim 1, wherein the at least one additional metal isselected from the group consisting of Pd, Pt, and Au.
 6. The process ofclaim 1, wherein the at least bidentate organic compound is selectedfrom the group consisting of 1,3,5-benzene tricarboxylate, acetylenedicarboxylate, naphtalen dicarboxylate, benzene dicarboxylate,adamantane tetracarboxylate, benzene tricarboxylate, benzenetribenzoate, methane tetrabenzoate, and adamantane tribenzoate.
 7. Theprocess of claim 1, wherein said catalyst further comprises at least onemonodentate ligand.
 8. The process of claim 7, wherein the monodentateligand is selected from the group consisting of alkyl amines havinglinear, branched, or cyclic aliphatic groups of from 1 to 20 carbonatoms, and alkyl ammonium salts thereof; aryl amines having from 1 to 5phenyl rings, and aryl ammonium salts thereof; alkyl phosphonium salts,having linear, branched, or cyclic aliphatic groups of from 1 to 20carbon atoms; aryl phosphonium salts having from 1 to 5 phenyl rings;alkyl organic acids having linear, branched, or cyclic aliphatic groupsof from 1 to 20 carbon atoms, and alkyl organic anions and saltsthereof; aryl organic acids having from 1 to 5 phenyl rings, and arylorganic anions and salts thereof; linear, branched, or cyclic aliphaticalcohols having from 1 to 20 carbon atoms; aryl alcohols having from 1to 5 phenyl rings; inorganic anions of the group consisting of sulfate,nitrate, nitrite, sulfite, bisulfite, phosphate, hydrogen phosphate,dihydrogen phosphate, diphosphate, triphosphate, phosphate, chloride,chlorate, bromide, bromate, iodide, iodate, carbonate, bicarbonate, andacids and salts thereof; and ammonia, carbon dioxide, methane, oxygen,ethylene, hexane, benzene, toluene, xylene, chlorobenzene, nitrobenzene,naphthalene, thiophene, pyridine, acetone, 1-2-dichloroethane,methylenechloride, tetrahydrofuran, ethanolamine, triethylamine andtrifluoromethylsulfonic acid.
 9. The process of claim 1, wherein themetal ion is Zn²⁺.
 10. The process of claim 1, wherein the metal-organicframework material is MOF-5.
 11. The process of claim 1, wherein thecatalyst has a pore size of from 0.2 to 30 nm.